Silvio R. Taffarel

Study of environmental pollution and mineralogical characterization of sediment rivers from Brazilian coal mining acid drainage

Acid drainage from coal mines and metal mining is a major source of underground and surface water contamination in the world. The coal mining acid drainage (CMAD) from mine contains large amount of solids in suspension and a high content of sulphate and dissolved metals (Al, Mn, Zn, Cu, Pb, Fe, etc.) that finally are deposited in the rivers. Since this problem can persist for centuries after mine abandonment, it is necessary to apply multidisciplinary methods to determine the potential risk in a determinate area. These multidisciplinary methods must include molecular and elemental analysis and finally all information must be studied statistically. This methodology was used in the case of coal mining acid drainage from the Tubarao River (Santa Catarina, Brazil). During molecular analysis, Raman Spectroscopy, electron bean, and X-ray diffraction (XRD) have been proven very useful for the study of minerals present in sediment rivers near this CMAD. The obtained spectra allow the precise identification of the minerals as jarosite, quartz, clays, etc. The elemental analysis (Al, As, Fe, K, Na, Ba, Mg, Mn, Ti, V, Zn, Ag, Co, Li, Mo, Ni, Se, Sn, W, B, Cr, Cu, Pb and Sr) was realised by inductively coupled plasma mass spectrometry (ICP-MS). Statistical analysis (Principal Component Analysis) of these dates of concentration reveals the existence of different groups of samples with specific pollution profiles in different areas of the Tubarao River.

Geochemistry of ultra-fine and nano-compounds in coal gasification ashes: A synoptic view

The nano-mineralogy, petrology, and chemistry of coal gasification products have not been studied as extensively as the products of the more widely used pulverized-coal combustion. The solid residues from the gasification of a low- to medium-sulfur, inertinite-rich, volatile A bituminous coal, and a high sulfur, vitrinite-rich, volatile C bituminous coal were investigated. Multifaceted chemical characterization by XRD, Raman spectroscopy, petrology, FE-SEM/EDS, and HR-TEM/SEAD/FFT/EDS provided an in-depth understanding of coal gasification ash-forming processes. The petrology of the residues generally reflected the rank and maceral composition of the feed coals, with the higher rank, high-inertinite coal having anisotropic carbons and inertinite in the residue, and the lower rank coal-derived residue containing isotropic carbons. The feed coal chemistry determines the mineralogy of the non-glass, non-carbon portions of the residues, with the proportions of CaCO₃ versus Al₂O₃ determining the tendency towards the neoformation of anorthite versus mullite, respectively. Electron beam studies showed the presence of a number of potentially hazardous elements in nanoparticles. Some of the neoformed ultra-fine/nano-minerals found in the coal ashes are the same as those commonly associated with oxidation/transformation of sulfides and sulfates.

Nano-mineralogical investigation of coal and fly ashes from coal-based captive power plant (India): an introduction of occupational health hazards.

Coal derived nano-particles has been received much concern recently around the world for their adverse effects on human health and the environment during their utilization. In this investigation the mineral matter present in some industrially important Indian coals and their ash samples are addressed. Coal and fly ash samples from the coal-based captive power plant in Meghalaya (India) were collected for different characterization and nano-mineralogy studies. An integrated application of advanced characterization techniques such as X-ray diffraction (XRD), High Resolution-Transmission Electron microscopy (HR-TEM)/(Energy Dispersive Spectroscopy) EDS/(selected-area diffraction pattern) SAED, Field Emission-Scanning Electron Microscopy (FE-SEM)/EDS analysis, and Mössbauer spectroscopy were used to know their extent of risks to the human health when present in coal and fly ash. The study has revealed that the coals contain mainly clay minerals, whilst glass fragments, spinel, quartz, and other minerals in lesser quantities were found to be present in the coal fly ash. Fly ash carbons were present as chars. Indian coal fly ash also found to contain nanominerals and ultrafine particles. The coal-fired power plants are observed to be the largest anthropogenic source of Hg emitted to the atmosphere and expected to increase its production in near future years. The Multi Walled Carbon Nano-Tubes (MWCNTs) are detected in our fly ashes, which contains residual carbonaceous matter responsible for the Hg capture/encapsulation. This detailed investigation on the inter-relationship between the minerals present in the samples and their ash components will also be useful for fulfilling the clean coal technology principles.

Effective removal of sulfur components from Brazilian power-coals by ultrasonication (40 kHz) in presence of H2O2

The present investigation reports a preliminary attempt of using ultrasonic energy (40kHz) to clean some low rank high sulfur Brazilian power-coal samples in presence of H2O2 solution. All types of sulfur components (i.e. pyritic, sulfate and organic) could be removed from the coal samples by this process. The raw and ultrasonicated coal samples were characterized by chemical analysis, Fourier Transformation Infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), focused ion beam (FIB), high-resolution transmission electron microscope (HR-TEM) with selected area electron diffraction (SAED) and/or microbeam diffraction (MBD), scanning transmission electron microscopy (STEM), energy-dispersive X-ray spectrometer (EDS), and Thermogravimetry (TG-DTG) techniques to evaluate the clean-coal quality. The FT-IR spectroscopic analysis demonstrated the formation of oxidized sulfur species (SO and -SO2) and their subsequent removals after ultrasonication. The XRD profiles supported the presence of mineral matters in the coals. The TG-DTG profiles of the beneficiated coals revealed their improved quality for using in thermal plants with better combustion efficiency.

Potential utilization for the evaluation of particulate and gaseous pollutants at an urban site near a major highway.

Works of particle number and mass concentration variability have a great importance since they may indicate better the influence of vehicle emissions in an urban region. Moreover, the importance of this work lies in the fact that there are few studies in Brazil, where the fuel used has unique characteristics. Consequently, this paper presents measurements of particle number (size range 0.3-10 μm), particle mass (PM10, PM2.5, PM1), O3 and NOx (NO, NO2), in a site near a major highway at the Metropolitan Area of Porto Alegre, south Brazil. Measurements were carried out during two years: 2012 and 2013. Particle number and mass concentrations were measured using an optical counter with a PM10 analyzer. Results showed that concentrations of N0.3-1 (0.3-1 μm) were the highest, although similar to N1-2.5 (1-2.5 μm). Daily variability of the analyzed pollutants followed the traffic pattern. Moreover, NO2, O3, and particle number were higher during the day, whereas NO, NOx, and particle matter showed higher concentrations during nighttime. Traffic influence was evidenced by the mean concentrations of weekends and weekdays, being higher for the latter. Correlation of particles and gases with meteorological variables, together with the application of PCA confirmed the influence of vehicle exhaust discharges.

Nano-mineralogy of suspended sediment during the beginning of coal rejects spill.

Ultrafine and nanometric sediment inputs into river systems can be a major source of nutrients and hazardous elements and have a strong impact on water quality and ecosystem functions of rivers and lakes regions. However, little is known to date about the spatial distribution of sediment sources in most large scale river basins in South America. The objective of this work was to study the coal cleaning rejects (CCRs) spill that occurred from a CCRs impoundment pond into the Tubarão River, South Brazil, provided a unique occasion to study the importance and role of incidental nanoparticles associated with pollutant dispersal from a large-scale, acute aquatic pollution event. Multifaceted geochemical research by X-ray diffraction (XRD), High Resolution-Transmission Electron microscopy (HR-TEM)/(Energy Dispersive Spectroscopy) EDS/(selected-area diffraction pattern) SAED, Field Emission-Scanning Electron Microscopy (FE-SEM)/EDS, and Raman spectroscopy, provided an in-depth understanding of importance of a nano-mineralogy approach of Aqueous Pollution Scenarios. The electron beam studies showed the presence of a number of potentially hazardous elements (PHEs) in nanoparticles (amorphous and minerals). Some of the neoformed ultrafine/nanoparticles found in the contaminated sediments are the same as those commonly associated with oxidation/transformation of oxides, silicates, sulfides, and sulfates. These data of the secondary ultra/nanoparticles, puts in evidence their ability to control the mobility of PHEs, suggesting possible presentations in environmental technology, including recuperation of sensitive coal mine. The developed methodology facilitated the sediment transport of the catchment providing consistent results and suggesting its usefulness as a tool for temporary rivers management.

Modification, adsorption, and geochemistry processes on altered minerals and amorphous phases on the nanometer scale: examples from copper mining refuse, Touro, Spain

The sulfide oxidation and precipitation of Al-Fe-secondary minerals associated with abandoned acid mine drainage (AMD) from the abandoned copper mine waste pile at Touro, Spain, has been studied by sequential extraction (SE) combined with several techniques with the intent of understanding the role of these processes play in the natural attenuation of hazardous element contaminants in the AMD. In addition, the fragile nature of nanominerals and ultrafine particle (UFP) assemblages from contaminated sediment systems from the abandoned copper mine required novel techniques and experimental approaches. The investigation of the geochemistry of complex nanominerals and UFP assemblages was a prerequisite to accurately assess the environmental and human health risks of contaminants and cost-effective chemical and biogeological remediation strategies. Particular emphasis was placed on the study and characterization of the complex mixed nanominerals and UFP containing potentially toxic elements. Nanometer-sized phases in sediments were characterized using energy-dispersive X-ray spectrometer (EDS), field-emission scanning electron microscope (FE-SEM), and high-resolution transmission electron microscopy (HR-TEM) images. The identification of the geochemical and mineralogical composition of AMD in Touro, as well as the different formation mechanisms proposed, complement the existing literature on secondary mineral assemblages and provide new emphasis to increase the understanding of extreme environments. The results also demonstrated that variations in the geochemical fractionation of hazardous elements in AMD were more influenced by the secondary mineral proportion and by AMD pH.

The properties of the nano-minerals and hazardous elements: Potential environmental impacts of Brazilian coal waste fire

Brazilian coal area (South Brazil) impacted the environment by means of a large number of coal waste piles emplaced over the old mine sites and the adjacent areas of the Criciúma, Urussanga, and Siderópolis cities. The area studied here was abandoned and after almost 30 years (smokeless visual) some companies use the actual minerals derived from burning coal cleaning rejects (BCCRs) complied in the mentioned area for industry tiles or refractory bricks. Mineralogical and geochemical similarities between the BCCRs and non-anthropogenic geological environments are outlined here. Although no visible flames were observed, this study revealed that auto-combustion existed in the studied area for many years. The presence of amorphous phases, mullite, hematite and other Fe-minerals formed by high temperature was found. There is also pyrite, Fe-sulphates (eg. jarosite) and unburnt coal present, which are useful for comparison purposes. Bad disposal of coal-dump wastes represents significant environmental concerns due to their potential influence on atmosphere, river sediments, soils and as well as on the surface and groundwater in the surroundings of these areas. The present study using advanced analytical techniques were performed to provide an improved understanding of the complex processes related with sulphide-rich coal waste oxidation, spontaneous combustion and mineral formation. It is reporting huge numbers of rare minerals with alunite, montmorillonite, szomolnokite, halotrichite, coquimbite and copiapite at the BCCRs. The data showed the presence of abundant amorphous Si-Al-Fe-Ti as (oxy-)hydroxides and Fe-hydro/oxides with goethite and hematite with various degrees of crystallinity, containing hazardous elements, such as Cu, Cr, Hf, Hg, Mo, Ni, Se, Pb, Th, U, Zr, and others. By Principal Component Analysis (PCA), the mineralogical composition was related with the range of elemental concentration of each sample. Most of the nano-minerals and ultra-fine particles found in the burned coal-dump wastes are the same as those commonly associated with coal cleaning rejects, in which oxidation of sulphides plays an important role to environment and human health.